Process for the distillation of alcohols

ABSTRACT

PCT No. PCT/EP96/00633 Sec. 371 Date Aug. 22, 1997 Sec. 102(e) Date Aug. 22, 1997 PCT Filed Feb. 14, 1996 PCT Pub. No. WO96/26173 PCT Pub. Date Aug. 29, 1996The invention relates to a process for the purification of C3-C10-alcohols by distillation, by distilling the alcohols at 150 to 200 DEG  C. in the presence of 10 to 1000 ppm of alkali metal hydroxide.

This application is the National Phase of international application PCT/EP96/00633, which has an international filing date of Feb. 14, 1996.

Aliphatic C₃ -C₁₀ -alcohols, such as n-butanol and, in particular, 2-ethylhexanol, have a high economic importance. These alcohols are preferably prepared by hydroformylation of olefins with subsequent hydrogenation of the aldehydes formed as intermediates (example: propylene→n/i-butyraldehyde→n/i-butanols) or by aldolization of straight-chain aliphatic aldehydes to give the corresponding unsaturated aldehydes and subsequent hydrogenation (example: n-butyraldehyde→2-ethylhexenal→2-ethylhexanol). Summary descriptions are found in, e.g., Ullmann's Encyclopedia of Industrial Chemistry: "Alcohols, Aliphatic" (Vol. A 1), "2-Ethylhexanol" (Vol. A 10) and "Butanols" (Vol. A 4).

Apart from as a solvent, n-butanol is principally used in the paints and coatings sector and for the preparation of carboxylic esters, in particular n-butyl acrylate and di-n-butyl phthalate (DBP).

2-Ethylhexanol is principally required as the alcohol component for the preparation of di-2-ethylhexyl phthalate (DEHP) and 2-ethylhexyl acrylate.

For these fields of application--in particular the preparation of acrylic ester--the use of high-purity alcohols is absolutely necessary. In the industrial preparation of the alcohols, the purification is exclusively performed by multistage fractional distillation. The alcohols in this case are exposed to a thermal stress over a period of several hours, bottom temperatures of 150 to 200° C. being generally employed. As a consequence thereof, in the distillation of aliphatic C₃ -C₁₀ -alcohols such as butanol and 2-ethylhexanol, formation of the corresponding aldehydes occurs which can be separated off only with high expenditure under conventional conditions employed in the technique.

The object was therefore to find a simple process for the distillation of C₃ -C₁₀ -alcohols which does not have these disadvantages.

Surprisingly, it has been found that addition of small amounts of alkali metal hydroxide suppresses the formation of the corresponding aldehydes during the workup by distillation and aldehydes already present are even eliminated.

The present invention therefore relates to a process for the purification of C₃ -C₁₀ -alcohols by distillation, which comprises distilling the alcohols at 150 to 200° C. in the presence of 10 to 1000 ppm of alkali metal hydroxide.

The C₃ -C₁₀ -alcohols can be straight-chain or branched. Particularly important C₃ -C₁₀ -alcohols, and more preferably C₄ -C₁₀ -alcohols to which the process of the invention can be applied are n-butanol and 2-ethylhexanol.

The alkali metal hydroxides used are preferably KOH or NaOH. The amount of alkali metal hydroxide is generally 10 to 1000 ppm, preferably 10 to 200 ppm, in each case based on the amount of the alcohol used. Preferably, the alkali metal hydroxides are added in the form of an aqueous solution.

If columns are used in the distillation, these generally have 20 to 80 trays.

As the following examples show, the addition of alkali metal hydroxide greatly decreases or even completely prevents the formation of aldehydes during the distillation of the alcohols, without other undesirable side reactions or significant reduction of the alcohol content occurring. Frequently, an aldehyde content already present in the alcohol used is even eliminated.

In the examples, the term "low-boilers" refers to components which are free of 2-ethylhexanal and boil considerably lower (at least 20 to 40° C. lower) than 2-ethylhexanol and may therefore readily be separated from this by distillation. Similarly, the term "high-boilers" refers to components which are free of 2-ethylhexanal and boil considerably higher (at least 20 to 40° C. higher) than 2-ethylhexanol and may therefore likewise readily be separated from this by distillation.

COMPARISON EXAMPLE 1

2-Ethylhexanol having a content of 60 ppm (0.006% by weight) of 2-ethylhexanal was heated at 180° C. for 1 hour without addition of alkali metal hydroxide. After 10, 30 and 60 minutes, a sample was taken in each case and analyzed. The results are given in Table 1. After 60 minutes, the 2-ethylhexanal content was 140 ppm (0.014% by weight).

EXAMPLE 1

The procedure was followed as in Comparison Example 1 with the sole exception that 50 ppm of KOH were added to the 2-ethylhexanol before heating was begun. The results are again given in Table 1. After 30 minutes, the 2-ethylhexanal content was already below the analytical detection limit of 0.001% by weight.

                                      TABLE 1                                      __________________________________________________________________________            Start-                                                                    ing                                                                            mat- Comparison Example                                                        erial (without alkali metal                                                    prior hydroxide) Example 1 (50 ppm KOH)                                        to Time after start Time after start                                                start                                                                              10 min                                                                             30 min                                                                              60 min                                                                             10 min                                                                             30 min                                                                              60 min                                        __________________________________________________________________________     Low-   0.216                                                                              0.212                                                                              0.211                                                                               0.212                                                                              0.208                                                                              0.209                                                                               0.207                                           boilers                                                                        (% by wt.)                                                                     2-Ethylhexanal 0.006 0.011 0.013 0.014 0.002 <0.001 <0.001                     (% by wt.)                                                                     2-Ethylhexanol 99.646 99.644 99.643 99.640 99.616 99.616 99.616                                                (% by wt.)                                     High- 0.132 0.133 0.133 0.134 0.174 0.175 0.177                                boilers                                                                        (% by wt.)                                                                   __________________________________________________________________________

COMPARISON EXAMPLE 2

663 g of 2-ethylhexanol of the composition below (in % by weight) are used in a 2 l distillation flask in a packed laboratory column having a 1 m high packing of 3 mm VA steel spirals:

    ______________________________________                                                Low-boilers                                                                             0.099                                                            2-Ethylhexanal 0.001                                                           2-Ethylhexanol 99.770                                                          High-boilers 0.130                                                           ______________________________________                                    

At a column pressure of 100 mbar and a reflux ratio of 3:1, four distillation fractions each of 130 g and a 5th fraction of 65 g were taken off at the column top at a temperature of 118° C. The individual fractions were studied by gas chromatography:

                  TABLE 2                                                          ______________________________________                                         Fraction                                                                              1        2        3      4       5                                      ______________________________________                                         Low-   0.010    0.006    0.003  0.011   0.008                                    boilers                                                                        (% by                                                                          wt.)                                                                           2-Ethyl- 0.013 0.009 0.008 0.010 0.011                                         hexanal                                                                        (% by                                                                          wt.)                                                                           2-Ethyl- 99.863 99.980 99.986 99.975 99.977                                    hexanol                                                                        (% by                                                                          wt.)                                                                           High- 0.114 0.005 0.003 0.004 0.004                                            boilers                                                                        (% by                                                                          wt.)                                                                         ______________________________________                                    

The 2-ethylhexanal content in the distillation residue (78 g) was below the analytical detection limit.

EXAMPLE 2

The procedure was followed as in Comparison Example 2, with the sole exception that 66 mg of a 50% strength aqueous KOH solution were added to the 2-ethylhexanol before the start of distillation. The individual fractions were again studied by gas chromatography:

                  TABLE 3                                                          ______________________________________                                         Fraction                                                                              1        2        3      4       5                                      ______________________________________                                         Low-   0.010    0.006    0.003  0.011   0.008                                    boilers                                                                        (% by                                                                          wt.)                                                                           2-Ethyl- 0.003 0.002 0.001 0.001 0.001                                         hexanal                                                                        (% by                                                                          wt.)                                                                           2-Ethyl- 99.863 99.987 99.993 99.984 99.987                                    hexanol                                                                        (% by                                                                          wt.)                                                                           High- 0.124 0.005 0.003 0.004 0.004                                            boilers                                                                        (% by                                                                          wt.)                                                                         ______________________________________                                    

The 2-ethylhexanal content in the distillation residue (78 g) was below the analytical detection limit. 

What is claimed is:
 1. A process for the purification of a C₄ -C₁₀ -alcohol by distillation from a distillation zone, said C₄ -C₁₀ -alcohol containing an aldehyde contaminant, said process comprising:distilling a C₄ -C₁₀ -alcohol at 150 to 200° C. in the presence of 10 to 200 ppm of alkali metal hydroxide, recovering from said distillation zone a C₄ -C₁₀ -alcohol having a decreased amount of said aldehyde contaminant wherein said alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
 2. The process as claimed in claim 1, wherein the C₄ -C₁₀ -alcohol in the distillation zone comprises n-butanol.
 3. The process as claimed in claim 1, wherein the C₄ -C₁₀ -alcohol in the distillation zone comprises 2-ethylhexanol.
 4. The process as claimed in claim 1, wherein the alkali metal hydroxide is in aqueous solution.
 5. The process as claimed in claim 4, wherein the contents of the distillation zone consist essentially of the C₄ -C₁₀ -alcohol and the alkali metal hydroxide.
 6. The process as claimed in claim 5, wherein said alkali metal hydroxide is potassium hydroxide.
 7. The process as claimed in claim 5, wherein said alkali metal hydroxide is sodium hydroxide.
 8. The process as claimed in claim 4, wherein said alkali metal hydroxide is potassium hydroxide.
 9. The process as claimed in claim 4, wherein said alkali metal hydroxide is sodium hydroxide.
 10. The process as claimed in claim 1, wherein the contents of the distillation zone consist essentially of the C₄ -C₁₀ -alcohol and the alkali metal hydroxide.
 11. The process as claimed in claim 10, wherein said alkali metal hydroxide is potassium hydroxide.
 12. The process as claimed in claim 10, wherein said alkali metal hydroxide is sodium hydroxide.
 13. The process as claimed in claim 1, wherein the alkali metal hydroxide suppresses the formation of any additional aldehyde contaminant.
 14. The process as claimed in claim 13, wherein said alkali metal hydroxide is potassium hydroxide.
 15. The process as claimed in claim 13, wherein said alkali metal hydroxide is sodium hydroxide.
 16. The process as claimed in claim 1, wherein said alkali metal hydroxide is potassium hydroxide.
 17. The process as claimed in claim 1, wherein the alkali metal hydroxide is sodium hydroxide.
 18. A process for the purification of 2-ethylhexanol, containing an aldehyde contaminant, by distillation from a distillation zone, said process comprising:distilling the 2-ethylhexanol at 150 to 200° C. in the presence of 10 to 200 ppm of potassium hydroxide, and recovering 2-ethylhexanol, containing a decreased amount of said aldehyde contaminant, from said distillation zone.
 19. A process for the purification of n-butanol, containing an aldehyde contaminant, by distillation from a distillation zone, said process comprising:distilling the n-butanol at 150 to 200° C. in the presence of 10 to 200 ppm of potassium hydroxide, and recovering n-butanol, containing a decreased amount of said aldehyde contaminant, from said distillation zone. 